Nanoscale solid-state polymeric battery system

ABSTRACT

The present invention relates to a unique polymeric battery system of electrochemical cells that are connected in series, and can be of nanometer size. The polymers possess conjugated bonds along their backbones and high levels of metals. The invention also concerns methods for the fabrication of the polymers and battery system as well as methods for the use of the polymers as a nanoscale solid-state battery.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. patent applications Ser.Nos. 60/304,054 (filed Jul. 10, 2001) and 60/242,463 (filed Oct. 23,2000), both of which applications are herein incorporated by referencein their entirety.

USE OF GOVERNMENTAL FUNDS

[0002] The present invention was funded in part through funds of theU.S. Government (ONR Contract No N00140010039). The U.S. Government mayhave certain rights in this invention.

FIELD OF THE INVENTION

[0003] The present invention relates to a unique polymeric batterysystem of electrochemical cells that are connected in series, and can beof nanometer size. The polymers possess conjugated bonds along theirbackbones and high levels of metals. The invention also concerns methodsfor fabrication of the polymers and battery system as well as methodsfor the use of the polymers as a nonscale solid-state battery.

BACKGROUND OF THE INVENTION

[0004] Batteries are devices that covert chemical energy within itsmaterial constituents into electrical energy. Three structuralcomponents are required for such transfer: the anode, or negativeelectrode material, which is oxidized, the electrolyte, which serves asa conductor of charged ions or electrons, and the cathode, or positiveelectrode, which is reduced. Chemical reactions at the electrodesproduce an electronic current that can be made to flow through anappliance connected to the battery. In a rechargeable (or “secondary”)battery, once the reactions have run their course, they can be reversedby the action of a power supply or charger. Desirable characteristics ofsecondary batteries include high power density, high discharge rates,flat discharge curves, and a good low-temperature performance.

[0005] The process of transferring electrons from one material toanother involves a redox reaction in which one material is reduced(thereby acquiring electrons) and another oxidized (thereby releasingelectrons). The choice of materials used to form a battery iscomplicated, and is affected by the chemistry of the redox reaction, aswell as by concerns relating to battery size, weight and cost, bypolarization, and by complications caused by reactivity with othercomponents(www.hrst.mit.edu/hrs/materials/public/Tutorial_solid_state_batteries.htm).The anode should be a good reducing agent, exhibit good conductivity andstability, and be easy and cheap to produce. Metals are most commonlyused as anodes. The lightest metal, lithium, has most often been chosen.Lithium is also very electropositive (so that combined with anelectronegative cathode, a large electromotive force will result). Theelectrolyte must be an insulator of electrons to prevent the batterycell from self-discharging. It also serves as a charge separator of thetwo electrodes. At the same time it must be an ionic conductor. Intypical batteries, the electrolyte is composed of a liquid such as waterhaving dissolved salts, acids or alkalis. Cathode materials areespecially important for the quality of the battery: the availableenergy of the battery is proportional to the cathode size and directlyrelated to many other characteristics.

[0006] The classical secondary battery contains two reversiblesolid-reactant electrodes and a liquid electrolyte: S⁻/L/S⁺. The Plantelead-acid cell commonly employed in car batteries is a typical example:Pb/H₂SO₄/PbO₂. During discharge, the so-called double sulphate reactionoccurs: Pb+PbO₂+2H₂SO₄→2PbSO₄+2H₂O (both electrodes are converted intolead sulphate) (see Visco et al., U.S. Pat. No. 5,516,598. The processesat the two electrodes involve dissolution and precipitation, as opposedto solid-state ion transport or film formation. The cadmium-nickelbattery used for heavy-duty tasks and emergency (standby) power is asecond example of a classical secondary battery. Sealed cadmium-nickelbatteries are widely used for smaller appliances, portable tools,electronic and photographic equipment, memory back-up etc. The basicelectrochemistry of discharge is: 2NiOOH+2H₂O+Cd→2Ni(OH)₂+Cd(OH)₂. Inthis discharge reaction, trivalent nickel hydroxide is reduced todivalent nickel hydroxide through the consumption of water, and metalliccadmium is oxidized into cadmium hydroxide. Liquid electrolyte batteriesare disclosed by Ventura et al. U.S. Pat. No. 5,731,104; Ventura et al.,U.S. Pat. No. 6,015,638.

[0007] In order to identify battery systems that might provide coupleelectrochemical properties with smaller size or weight, researchers havelong sought to define suitable solid-state battery systems. Solidelectrolytes are of particular interest for secondary batteries and forfuel cells (www.web.mit.edu/newsoffice/tt/1998/apr29/battery.html;Munshi M Z A (ed.), “Handbook Of Solid-state Batteries And Capacitors,”Intermedics Inc., USA, (1995). The first such system (asodium/sodium-β-alumina/sulfur battery) was developed in 1967, and useda polycrystalline ceramic (b-alumina) to conduct sodium ions attemperatures above 350° C. Unresolved problems, including high failurerates, the short lifetime of the ceramic electrolyte and lack ofreproducibility have limited the utility of such batteries.

[0008] Reversible lithium solid-state batteries have been developed inwhich an anode of metallic lithium is separated from the cathode (anintercalation compound such as titanium disulfide or lithium cobaltoxide) by a glass electrolyte. One advantage of this type of battery isthat the overall resistance does not increase with discharge. Theelectromotive force (emf) is approximately 2V (this emf can vary widelywith cathode materials) with only a slight and continuous decrease withloss of capacity. This contrasts with conventional batteries, whichexperience an abrupt loss of voltage without warning upon depletion. Forexample, such batteries may contain an anode having lithium betweengraphitic coke layers, an amorphous polymer electrolyte (such asLiCoO₂/El/carbon; LiNiO₂/El/carbon; or LiNi_(0.2)CoO_(0.8)/El/carbon).Although lithium cobalt oxide (CoO₂) is similar to titanium sulfide(TiS₂)in structure and behaviour, it is much more oxidizing than TiS₂,and thus produces a cell having an emf of about 3.5V, almost three timesas much as a nickel-cadmium or nickel-hydride battery. Secondary lithiumbatteries are discussed by Iwamoto et al. (U.S. Pat. No. 5,677,081) andTakada et al. (U.S. Pat. No. 6,165,646). Additional information relevantto efforts to define improved battery systems is disclosed in WO9719481,WO09514311; WO09533863; WO09507555; WO09413024; WO09120105, and inAbraham et al., U.S. Pat. Nos. 5,510,209 and 5,491,041.

[0009] Polymeric compounds have also been used in batteries (see, e.g.,Narang et al., U.S. Pat. Nos. 5,998,559 and 5,633,098, which describethe formation of batteries having a single-ion electrolyte through theuse of functionalized polysiloxanes, polymethacrylates and poly(alkyleneoxides). Takeuchi et al. (U.S. Pat. Nos. 5,874,184 and 5,665,490)discloses a battery having a solid polymer electrolyte comprising acomposite of a polymeric component (see also, Narang et al. U.S. Pat.No. 5,548,055. Polymeric compounds used in batteries are also discussedby Llompart, S. et al., “Oxygen-Regeneration of Discharged ManganeseDioxide Electrode II-General Phenomena Observed on Electro-DepositedLayer Electrodes and Membrane Electrodes,” J. Electrochem. Soc., Vol.138 (No. 3), page 665 (1991); see also Takeuchi, et al. (U.S. Pat. No.5,597,661).

[0010] Despite such efforts, a need remained to find materials with highconductivity at ambient temperatures. High molecular weight polyethyleneoxide hosts with lithium salts, polyvinyl ether hosts, and electrolytesformed by trapping a low molecular weight liquid solution of a lithiumsalt in an aprotic organic solvent, within the polymer matrix of a highmolecular weight material have all been explored in a search forsuitable materials.

[0011] In particular, conventional, liquid electrolyte batteries havesignificant drawbacks, particularly for electronics. These disadvantagesinclude weight, large size, and the possibility that the electrolytemight leak. In addition, as computers and mobile phones have becomesmaller and faster, their demands for battery power have increased.Although solid-state batteries typically have a lower-power density thanconventional batteries, they exhibit improved energy density, are reeasily miniaturized (even as thin films), and cannot leak. In additionthey are long-lived and their performance does not markedly change athigh or low temperatures. For these reasons, solid-state batteries arewell suited for electronic devices. The present configurations ofsolid-state battery have a liquid or gel electrolyte between the anodeand cathode. Unfortunately, such battery configurations lead to problemsinvolving electrolyte loss and decreased performance over time. A needtherefore exists for improved solid-state battery systems. The presentinvention addresses this and other needs.

SUMMARY OF THE INVENTION

[0012] The present invention relates to a unique polymeric batterysystem of electrochemical cells that are connected in series, and can beof nanometer size. The polymers possess conjugated bonds along theirbackbones and high levels of metals. The invention also concerns methodsfor the fabrication of the polymers and battery system as well asmethods for the use of the polymers as a nanoscale solid-state battery.

[0013] In detail, the invention comprises an anode of a solid-statebattery comprising an organometallic polymer of the structure:

[0014] wherein n′ is greater than 50 (and preferably greater than 100),and R is a divalent and/or transition metal (such as Co, Mn, Zn, etc.),or an alkali earth metal atom or is two monovalent metals or alkaliearth metals.

[0015] The invention particularly concerns the embodiment of such anode,wherein the organometallic polymer has the structure:

[0016] The invention further concerns the embodiment of such anode,wherein the polymer is produced through the polymerization of a monomerhaving the structure:

[0017] wherein R is a divalent and/or transition metal (such as Co, Mn,Zn, etc.), or an alkali earth metal atom or is two monovalent metals oralkali earth metals, such as, wherein the monomer has the structure:

[0018] The invention further concerns a cathode of a solid-state batterycomprising a polymer having the structure:

[0019] wherein n′″ is greater than 50, and wherein R1, R2, R1′ and R2′are polar substituent groups that may be used to coordinate and formeither ionic or covalent bonds with metals or metal oxides, and may bethe same or different R1 and R2 will preferably be selected from thegroup consisting of TMS, CH3, H, or Na; R1′ and R2′ will preferably beselected from the group consisting of or may be OTMS, OCH₃, OH, ONa, andNH₃. OCH₃ is a peroxide that is unstable in water, and will decompose toOH.

[0020] The invention further concerns the embodiment of such cathode,wherein the polymer is produced through the polymerization of a monomerhaving the structure:

[0021] wherein R1 and R2 are polar substituent groups that may be usedto coordinate and form either ionic or covalent bonds with metals ormetal oxides, and may be the same or different. R1 and R2 willpreferably be selected from the group consisting of TMS, OCH₃, OH, ONa,and CH₃.

[0022] The invention further provides a solid-state battery systemcomprising a battery comprising an anode polymer connected to anelectrolyte polymer, wherein the anode polymer has the structure:

[0023] wherein n′ is greater than 50, and R is a divalent metal oralkali earth metal atom or is two monovalent metals or alkali earthmetals; and wherein the electrolyte polymer is a polyethylene oxide(PEO) polymer having the structure:

[0024] wherein n″ is greater than 50.

[0025] The invention further concerns the embodiment of such batterysystem wherein the anode polymer has the structure:

[0026] The invention further a solid-state battery system comprising abattery comprising a cathode polymer connected to an electrolytepolymer, wherein the cathode polymer has the structure:

[0027] wherein n′″ is greater than 50, and wherein R1 and R2 may be thesame or different, and are selected from the group consisting of TMS,CH3, H, or Na;

[0028] wherein R1′ and R2′ may be the same or different, and areselected from the group consisting of or may be OTMS, OCH₃, OH, ONa, andNH₃ (the additional oxygen would make an unstable peroxy-type compound,and thus the non-peroxy variant is preferred); and wherein theelectrolyte polymer is a polyethylene oxide (PEO) polymer having thestructure:

[0029] wherein n″ is greater than 50. The PEO electrolyte can alsooptionally have a metal or metal oxide filler, which has been shown toenhance low temperature ionic conductivity. This metal or metal oxidefiller can be blended in using standard polymer processing techniques.

[0030] The invention further concerns a solid-state battery systemcomprising a battery comprising an anode polymer connected to anelectrolyte polymer, which is connected to a cathode polymer, whereinthe anode polymer has the structure:

[0031] wherein n′ is greater than 50, and R is a divalent and/ortransition metal metal or an alkali earth metal atom or is twomonovalent metals or alkali earth metals; wherein the electrolytepolymer is a polyethylene oxide (PEO) polymer having the structure:

[0032] wherein n″ is greater than 50; and wherein the cathode polymerhas the structure:

[0033] wherein n′″ is greater than 50, and wherein R1 and R2 may be thesame or different, and are selected from the group consisting of TMS,CH3, H, or Na;

[0034] wherein R1′ and R2′ may be the same or different, and areselected from the group consisting of or may be OTMS, OCH₃, OH, ONa, andNH₃.

[0035] The invention further concerns the embodiment of such batterysystem wherein the anode polymer has the structure:

[0036] The invention further concerns the embodiment of all such batterysystems wherein the battery is a film, coating or sheet.

[0037] The invention also concerns a computer powered by a batterysystem comprising a battery comprising an anode polymer connected to anelectrolyte polymer, which is connected to a cathode polymer, whereinthe anode polymer has the structure:

[0038] wherein n′ is greater than 50, and R is a divalent metal oralkali earth metal atom or is two monovalent metals or alkali earthmetals; wherein the electrolyte polymer is a polyethylene oxide (PEO)polymer having the structure:

[0039] wherein n″ is greater than 50; and wherein the cathode polymerhas the structure:

[0040] wherein n′″ is greater than 50, and wherein R1 and R2 may be thesame or different, and are selected from the group consisting of TMS,CH3, H, or Na;

[0041] wherein R1′ and R2′ may be the same or different, and areselected from the group consisting of or may be OTMS, OCH₃, OH, ONa, andNH₃.

[0042] The invention further concerns the embodiment of such computerwherein the anode polymer has the structure:

[0043] The invention further concerns the embodiment of all suchcomputers wherein the computer is a cellular telephone, pager, ortwo-way radio, or is a personal computer, PDA, or laptop computer, or isa global positioning system or camera.

BRIEF DESCRIPTION OF THE FIGURES

[0044]FIG. 1 illustrates the arrangement of one embodiment of the A, B,and C Block polymers of a solid-state battery of the present invention.

[0045]FIG. 2 illustrates the arrangement of a second embodiment of theA, B, and C Block polymers of a solid-state battery of the presentinvention.

[0046]FIG. 3 illustrates the arrangement of a third embodiment of the A,B, and C Block polymers of a solid-state battery of the presentinvention.

[0047]FIG. 4 illustrates the structure of an A/B/C triblock copolymerfor an organometallic lithium A Block polymer, and its epoxidation inthe presence of a Mg organic salt.

[0048]FIG. 5 illustrates the structure of an A/B/C triblock copolymerfor an organometallic cobalt A Block polymer.

[0049]FIG. 6 illustrates the structure of an A/B and B/C diblockcopolymer for an organometallic cobalt A Block polymer.

[0050]FIG. 7 shows the NMR spectra of the norbomene diamine precursorand of a norbornene-Co monomer.

[0051]FIG. 8 shows the NMR spectra of an A Block homopolymer ofnorbornene-Co.

[0052]FIG. 9 shows the NMR spectra of a tetraoxacyclodecene B Blockmonomer.

[0053]FIG. 10 shows the NMR spectra of a C Block monomer norbomenecarboxylic acid trimethylsilane.

[0054]FIG. 11 shows the GPC analysis of a C Block Homopolymer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0055] I. The Unique Polymeric Battery Systems of The Present Invention

[0056] The present invention relates to unique polymeric battery systemsof electrochemical cells that are connected in series, and can be ofnanometer size.

[0057] As used herein, the term “battery” refers to an electrochemicalcell, capable of generating current, or storing chemical energy,composed of an anode in contact with an electrolyte, in contact with acathode. As used herein, the term “battery system” refers to a batteryor to a device, such as a capacitor, capable of generating current,which may additionally comprise leads or other connectors for chargingor discharging the battery, or which may additionally comprise housings,cases, covers, etc.

[0058] The polymers of the battery systems of the present inventionpossess conjugated bonds along their backbones and high levels ofmetals. The invention also concerns methods for the fabrication of thepolymers and battery system as well as methods for the use of thepolymers as a nanoscale solid-state battery.

[0059] In particular, the present invention relates to an A/B/C“triblock” copolymer—metal nanocomposite, and to methods for itsfabrication and use as a nanoscale solid-state battery. Preferably, theA/B/C triblock copolymer will exhibit a lamellar microphase separation,in which the A block polymer forms the anode, the B block polymer formsa polymeric electrolyte and the C block polymer forms the cathode.Casting of the synthesized polymer from a solvent can be conducted so asto result in a self-assembled lamellar A/B/C nanostructure, which isequivalent to many battery cells in series. The A, B, and C Blocks arechemically linked, but are exhibit a microphase separation due to blockincompatibility, crystallization, etc. They can be used as templates forthe synthesis of metal and metal oxide nanoclusters through variousprocesses including, but not limited to, metal salt introduction andsubsequent reduction and/or oxidation by chemical means.

[0060] The A/B/C/ Block copolymers of the present invention arepreferably produced as a film, coating or sheet. In one embodiment, asingle layer of each Block polymer will be employed (see FIG. 1).Alternatively, such films, coatings or sheets may be produced havingmore than a single layer of each Block polymer (see FIG. 2). In yetanother embodiment, the film, coating or sheet may be prepared using A/Band B/C diblocks (see FIG. 3). The spaces shown between adjacentpolymers in FIGS. 1-3 are merely to illustrate the polymeric A/B/C, etc.structure of the polymers; adjacent polymers may, and preferably will,contact one another.

[0061] A. The A Block Polymer

[0062] The A Block polymer of the present invention is preferablycomposed of an organometallic metal polymer. Suitable organometallicmetal polymers include organometallic lithium polymers (e.g., polymerscomposed of a lithium amido end-capped norbornene monomer), and morepreferably, organometallic cobalt polymers (e.g., cobaltamidonorbornene), however other similar organometallic metal monomersmay be employed:

[0063] 1. Lithium Amido End-Capped Norbornene Monomer

[0064] Synthesis of a lithium amido end-capped norbomene A Block monomercan be preferably accomplished with a Diels-Adler reaction betweencyclopentadiene and fumarate to produce norbornene-5,6 carboxylic acid.The carboxylic acid is then reduced with AlLiH₄/ether to form2-norborene dimethyl alcohol. The dialcohol is protected from furtherreaction with p-tolunesulfonyl chloride (in pyridine). Thetolunesulfonyl chloride is displaced by t-butyl amine (t-Bu; DMF, 24hours) to allow for chelation with lithium. n-butyl lithium is reactedwith the t-butyl amine (−40° C., pentane)to form the lithium amidoend-capped norbornene monomer:

[0065] 2. Cobalt Amidonorbornene Monomer

[0066] As indicated above, A Block polymers composed of organometalliccobalt are preferred over organometallic lithium. The use oforganometallic cobalt is associated with greater stability and improvedproperties.

[0067] The cobalt amidonorbornene monomer can be synthesized through aDiels-Adler reaction between cyclopentadiene and dimethyl fumarate toproduce norbornene-5,6 dimethyl ester. The dimethyl ester is thenreduced with AlLiH₄/THF to form 2-norborene dimethyl alcohol. Thedialcohol is protected from further reaction with p-tolunesulfonylchloride (in pyridine). The tolunesulfonyl chloride is displaced byt-butyl amine (t-Bu; DMF, 24 hours) to allow for chelation with lithium.n-butyl lithium is reacted with the t-butyl amine (−40° C., pentane)toform the lithium amido end-capped norbornene monomer. The compound isthen reacted with CoCl2 at −40° C. in ether to form the desiredorganometallic cobalt compound:

[0068] Note that in the above-described synthesis of the lithium amidoend-capped monomer the COOH group is soluble in THF; in contrast, theabove-described synthesis of the cobalt amidonorbomene monomer employsthe dimethyl ester which is easier to purify.

[0069] The A Block monomers can be polymerized with (PYC₃)₂Cl₂Ru═CHR(“Grubb's Catalyst” (THF)) or Shrock's catalyst:

Mo(C₁₀H₁₂)(C₁₂H₁₇N)[OC(CH₃)(CF₃)₂]₂

[0070]

[0071] Polymerization of the organometallic lithium A Block monomeryields the following polymer:

[0072] Polymerization of the organometallic cobalt A Block monomeryields the following polymer, which in the presence of water reacts toform CoO, as shown:

[0073] Any desired number of monomers can be employed in such polymers.Preferably, the A Block polymer will have an approximate molecularweight of greater than 10,000, and more preferably greater than 100,000.

[0074] B. The B Block Polymer

[0075] The B Block polymer of the present invention is preferably apolyethylene oxide (PEO). The monomer can be prepared from a ringclosing metathesis (RCM) reaction to form an unsaturated crown etheranalog, such as 12, 4 crown ether with a double bond at the carbon 1position (tetraoxacyclodecene):

[0076] The B Block polymer is preferably formed from norbomene-5,6dimethyl ester monomers. The monomer used in this block polyethyleneoxide (PEO). The monomer can be prepared from a ring closing metathesis(RCM) reaction to form an unsaturated crown ether analog, such as 12, 4crown ether with a double bond at the carbon 1 position.

[0077] Alternatively, the unsaturated crown ether analog may besynthesized as follows:

[0078] Polymerization can be performed with Grubb's catalyst andSchrock's catalyst, with molecular weights of each block of 50 kDa.Residual ruthenium from the deactivated catalyst would isomerize themonomer during distillation, encumbering polymerization. To avoid thisproblem, a water-soluble phosphine can be employed to remove theruthenium and allow the monomer to be purified:

[0079] Any desired number of monomers can be employed in such polymers.Preferably, the B Block polymer will have an approximate molecularweight of greater than 10,000, and more preferably greater than 100,000.

[0080] In addition, the unique form of the ROMP derived PEO allowsseveral subsequent reactions to be performed on the double bonds.Epoxidation and hydrolysis of the double bonds can give rise to variousfunctionalities along the backbone of the PEO, including, but notlimited to: OH, CF₃SO₃ (triflate salt), OCH₃.

[0081] C. The C Block Polymer

[0082] The C Block polymer of the present invention is preferablycomposed of a functionalized norbornene (such as poly(norbomenecarboxylic acid)) and utilizes a hydride reduction. The monomer can be anorbornene 5,6 dimethyl ester:

[0083] Such a monomer can be formed as shown below:

[0084] More preferably, such a monomer can be formed using the followingscheme:

[0085] Upon polymerization, C Block polymers of such a monomer will havethe following structure:

[0086] This material can be incorporated as MnCl₂ with LiCl andhydrolyzed and oxidized with water:

[0087] In an alternative embodiment, the C Block polymer can be a poly(norbornene 5,6, trimethylsilane). The monomer for such a polymer hasthe structure:

[0088] Such a monomer can be formed as shown below:

[0089] Upon polymerization, C Block polymers of such a monomer will havethe following structure:

[0090] This polymer may be processed to incorporate lithium as shownbelow:

[0091] Alternatively, other cathode materials, such as TiS₂ andLiMn2−xCo_(x)O₄ may be employed. These materials will be incorporated asinorganic salts, then reacted to form nanoparticles in the phaseseparated domains of the C Block. Verification of the chemical structurecan be obtained using NMR and the molecular weight of the polymer can bedetermined by GPC.

[0092] Any desired number of monomers can be employed in such polymers.Preferably, the C Block polymer will have an approximate molecularweight of greater than 10,000, and more preferably greater than 100,000.

[0093] The general structure of a triblock polymer using a lithium amidoend-capped norbomene monomer as the basis for the A Block polymer, andits epoxidation in the presence of an Mg organic salt, are shown in FIG.4. The general structure of a triblock polymer using a cobalt norbornenemonomer as the basis for the A Block polymer is shown in FIG. 5. InFIGS. 4 and 5, n′, n″, and n′″ denote the number of monomer units ofeach of the A, B, and C Block polymers respectively, and may be the sameor different, and may vary independently of one another. Polymerizationoccurs sequentially, for example, the A Block monomer is polymerized,then the B Bblock monomer is added to the “living A chain,” to add a BBlock polymer, then a C block monomer is added to the “living AB chain,”to form the ABC triblock polymer.

[0094] II. Production and Uses of the Unique Polymeric Battery System ofthe Present Invention

[0095] In conventional liquid electrolyte batteries, most ions conductcurrent, and therefore high conductivity is exhibited. Conventionalbatteries have, however, no long-range order and are not selectivetowards different ions. In contrast, the solid-state batteries of thepresent invention employ mostly alkali earth ions to conduct current.Conductivity is temperature dependent, and may operate due to thelong-range order of the polymer blocks within the triblock arrangementof polymers. Additionally, the batteries of the present invention canoperate through the conductance of a single ionic species. The batteryfunctions better at elevated temperature, due mostly to the increasedionic conductivity of the PEO.

[0096] The polymer battery systems of the present invention have theadvantage that they can be produced as thin films, coatings, sheets,etc. that can be wound into coils or processed as sheets to formbatteries. In one embodiment of the invention, such battery systems willbe configured as an A/B/C triblock (see, for example, FIG. 1),alternatively other configurations, such as an A/B/C/B/A pentablock(see, for example, FIG. 2), or as one or more series of A/B and B/Cdiblocks (see, for example, FIG. 3). Such diblocks configurations may befixed in contiguous contact, such that the A, B and C polymers permit anelectrical current to flow. Alternatively, the diblock configurationscan be configured so as to be positionable with respect to one anothersuch that electrical current will not flow until the diblocks are placedin contact with one another (i.e., as a capacitor to effect currentflow).

[0097] The polymer battery systems of the present invention may comprisesingle batteries, or may comprise two or more batteries connected to oneanother in series or in parallel in order to provide enhanced voltage orcurrent.

[0098] Due to the absence of liquid electrolytes, the formed sheets arenot subject to leakage, and thus are more reliable than conventionalbatteries. Additionally, they may be used to position the power sourcenear devices or circuits that are to be powered by the battery, therebyreducing the amount of wiring, levels of interconnects, and resistancelosses associated with operating the device.

[0099] The devices that can be made using the polymers of the presentinvention preferably comprise a polymer in which the electrodes arepowered through the polymer chain. A top electrode that is miscible withthe anode and an electrode specific for the cathode allows forrecharging of the battery. Such film, coating or sheet may be discretefrom the structure of the device being powered (as is the case forstandard batteries), or may be fashioned so as to be integral to thestructure of the device. For example, the battery systems of the presentinvention can be fused, deposited or otherwise associated with thehousing or case of a device (e.g., the plastic housing of a portabletelephone), or with a structural component of the device (e.g., aportion of the frame, etc. of an automobile).

[0100] The electrochemically driven size confinement of the metalparticles of the batteries of the present invention enhanceselectrochemical activity, and provides the battery with better cyclingperformance (i.e., performance upon repeated charging and discharging).The reduced electrochemical cell length of the batteries of the presentinvention improves conductivity relative to conventional batteries.

[0101] In one embodiment, such battery systems will comprise leads orother connectors to permit the recharging of the battery. Alternatively,the battery systems may be configured as disposable power sources,lacking such leads.

[0102] The battery systems of the present invention have particularutility in powering solid-state devices, such as computers, radios,televisions, DVD playersetc., but may also be used to power any otherelectrically powered device. As used herein the term “computer” isintended to refer not only to conventional mainframe, personalcomputers, or laptop computers (i.e. mobile personal computers), butalso to any device capable of processing or storing digital data (e.g.,personal digital assistants (PDAs), global positioning systems, pagers,two-way radios, telephones (especially cellular telephones), cameras(still picture, motion picture or broadcast), etc.). In one embodiment,such battery systems will be employed as the main power source, so as torender the device portable. Alternatively, the battery systems of thepresent invention may be employed as a “back-up,” or auxiliary powersource.

[0103] Having now generally described the invention, the same will bemore readily understood through reference to the following examples,which are provided by way of illustration, and are not intended to belimiting of the present invention, unless specified.

EXAMPLE 1

[0104] A/B/C Triblock Polymer Using a Lithium Amido End-CappedNorbornene Monomer

[0105] To illustrate the present invention, an A/B/C triblock polymerusing a lithium amido end-capped norbornene monomer as the basis for theA Block polymer, polyethylene oxide (PEO) as the B Block polymer, andpoly(norbornene carboxylic acid)) as the C Block polymer.

[0106] The Li-capped monomer provides a phase-separated domaincontaining lithium to act as the anode. The electrochemical cellreactions of the battery involve the formation of lithium at thecathode: Li⁺+e⁻→Li, and the formation of lithium ion at the anode:Li→Li⁺+e⁻, so as to produce a direct current. The A Block polymerprovides the lithium metal, the B Block polymer provides theelectrolyte, and the C Block polymer provides Li_(x)→Mn₂O₄ so that theoverall electrochemical cell reaction is: Li_(x)→Li_(1−x)Mn₂O₄;E_(cell)=3.60 V.

[0107] The individual A, B, and C Block polymers are prepared asdescribed above. The Anode Block has an approximate molecular weight of400,000; the Electrolye Block has an approximate molecular weight of500,000; the Cathode Block has an approximate molecular weight of400,000.

[0108] A battery having a surface of 9 cm² and a thickness of 100 μM isprepared. Assuming that the cells have lamellae of 300 Å, conductivitiesof: σ_(A)=2×10⁻¹⁰ S/cm, σ_(B)=4×10⁻⁵ S/cm, σ_(C)=2×10⁻¹⁰ S/cm areattained. The predicted charge capacity of the battery is 5.15 mAH/g ofmaterial.

EXAMPLE 2

[0109] A/B/C Triblock Polymer Using a Cobalt Norbornene Monomer

[0110] To illustrate the present invention, an A/B/C triblock polymerusing a cobalt norbomene monomer as the basis for the A Block polymer,polyethylene oxide (PEO) as the B Block polymer, and poly(norbornenecarboxylic acid)) as the C Block polymer. The cathode reaction of thebattery is:

2LiMn₂O₄

2Li⁺+4MnO₂+2e⁻

[0111] The anode reaction of the battery is:

CoO+2Li⁺+2e⁻

Li₂O+Co

[0112] Thus, lithium ions flow to the A Block polymer, and electronsflow to the C Block polymer. The formation and decomposition of lithiumdioxide is fully reversible. The battery employs an electrochemicallydriven size confinement of metal particles to enhance activity andprovide better battery cycling performance.

[0113]FIG. 7 shows the NMR spectra of the norbornene diamine precursorand of the A Block norbornene-Co monomer. FIG. 8 shows the NMR spectraof the A Block homopolymer of norbomene-Co. FIG. 9 shows the NMR spectraof the tetraoxacyclodecene B Block monomer. FIG. 10 shows the NMRspectra of the C Block monomer norbomene carboxylic acidtrimethylsilane. FIG. 11 shows the GPC analysis of the C BlockHomopolymer. The Figure plots the relative response vs. time in minutes.The polymer had an M_(n)=362,185, a M_(w)=597,050, and a PDI of 1.64.

[0114] A battery having a surface of 9 cm² and a thickness of 100 μM isprepared. Assuming that the battery had a 300 Å lamellae and no metalloading, conductivities of: σ_(A)=2×10⁻¹⁰ S/cm, σ_(B)=4×10⁻⁵ S/cm,σ_(c)=2×10⁻¹⁰ S/cm are attained. The battery had a 3.6 V source. Thepredicted charge capacity of the battery is 5.15 mAH/g of material.

[0115] All publications and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication or patent application had beenspecifically and individually indicated to be incorporated by reference.The discussion of the background to the invention herein is included toexplain the context of the invention. Such explanation is not anadmission that any of the material referred to was published, known, orpart of the prior art or common general knowledge anywhere in the worldas of the priority date of any of the aspects listed above.

[0116] While the invention has been described in connection withspecific embodiments thereof, it will be understood that it is capableof further modifications and this application is intended to cover anyvariations, uses, or adaptations of the invention following, in general,the principles of the invention and including such departures from thepresent disclosure as come within known or customary practice within theart to which the invention pertains and as may be applied to theessential features hereinbefore set forth.

What is claimed is:
 1. An anode of a solid-state battery comprising anorganometallic polymer of the structure:

wherein n′ is greater than 50, and R is a divalent and/or transitionmetal or an alkali earth metal atom or is two monovalent metals oralkali earth metals.
 2. The anode of claim 1, wherein saidorganometallic polymer has the structure:


3. The anode of claim 1, wherein said polymer is produced through thepolymerization of a monomer having the structure:

wherein R is a divalent metal or alkali earth metal atom or is twomonovalent metals or alkali earth metals.
 4. The anode of claim 3,wherein said monomer has the structure:


5. The anode of claim 1, wherein n′ is 100 or more.
 6. A cathode of asolid-state battery comprising a polymer having the structure:

wherein n′″ is greater than 50, and wherein R1 and R2 may be the same ordifferent, and are selected from the group consisting of TMS, CH3, H, orNa; wherein R1′ and R2′ may be the same or different, and are selectedfrom the group consisting of or may be OTMS, OCH₃, OH, ONa, and NH₃. 7.The cathode of claim 6, wherein said polymner is produced through thepolymerization of a monomer having the structure:

wherein R1 and R2 may be the same or different, and are selected fromthe group consisting of TMS, OCH₃, OH, ONa, and CH₃.
 8. A solid-statebattery system comprising a battery comprising an anode polymerconnected to an electrolyte polymer, wherein said anode polymer has thestructure:

wherein n′ is greater than 50, and R is a divalent and/or transitionmetal or an alkali earth metal atom or is two monovalent metals oralkali earth metals; and wherein said electrolyte polymer is apolyethylene oxide (PEO) polymer having the structure:

wherein n″ is greater than
 50. 9. The battery system of claim 8, whereinsaid anode polymer has the structure:


10. A solid-state battery system comprising a battery comprising acathode polymer connected to an electrolyte polymer, wherein saidcathode polymer has the structure:

wherein n′″ is greater than 50, and wherein R1 and R2 may be the same ordifferent, and are selected from the group consisting of TMS, CH3, H, orNa; wherein R1′ and R2′ may be the same or different, and are selectedfrom the group consisting of or may be OTMS, OCH₃, OH, ONa, and NH₃, andwherein said electrolyte polymer is a polyethylene oxide (PEO) polymerhaving the structure:

wherein n″ is greater than
 50. 11. A solid-state battery systemcomprising a battery comprising an anode polymer connected to anelectrolyte polymer, which is connected to a cathode polymer, whereinsaid anode polymer has the structure:

wherein n′ is greater than 50, and R is a divalent and/or transitionmetal or an alkali earth metal atom or is two monovalent metals oralkali earth metals; wherein said electrolyte polymer is a polyethyleneoxide (PEO) polymer having the structure:

wherein n″ is greater than 50; and wherein said cathode polymer has thestructure:

wherein n′″ is greater than 50, and wherein R1 and R2 may be the same ordifferent, and are selected from the group consisting of TMS, CH3, H, orNa; wherein R1′ and R2′ may be the same or different, and are selectedfrom the group consisting of or may be OTMS, OCH₃, OH, ONa, and NH₃. 12.The battery system of claim 11, wherein said anode polymer has thestructure:


13. The battery system of claim 8, wherein said battery is a film,coating or sheet.
 14. The battery system of claim 10, wherein saidbattery is a film, coating or sheet.
 15. The battery system of claim 11,wherein said battery is a film, coating or sheet.
 16. The battery systemof claim 12, wherein said battery is a film, coating or sheet.
 17. Acomputer powered by a battery system comprising a battery comprising ananode polymer connected to an electrolyte polymer, which is connected toa cathode polymer, wherein said anode polymer has the structure:

wherein n′ is greater than 50, and R is a divalent and/or transitionmetal or an alkali earth metal atom or is two monovalent metals oralkali earth metals; wherein said electrolyte polymer is a polyethyleneoxide (PEO) polymer having the structure:

wherein n″ is greater than 50; and wherein said cathode polymer has thestructure:

wherein n′″ is greater than 50, and wherein R1 and R2 may be the same ordifferent, and are selected from the group consisting of TMS, CH3, H, orNa; wherein R1′ and R2′ may be the same or different, and are selectedfrom the group consisting of or may be OTMS, OCH₃, OH, ONa, and NH₃. 18.The computer of claim 17, wherein said anode polymer has the structure:


19. The computer of claim 17, wherein said computer is a cellulartelephone, pager, or two-way radio.
 20. The computer of claim 18,wherein said computer is a cellular telephone, pager, or two-way radio.21. The computer of claim 17, wherein said computer is a personalcomputer, PDA, or laptop computer.
 22. The computer of claim 18, whereinsaid computer is a personal computer, PDA, or laptop computer.
 21. Thecomputer of claim 17, wherein said computer is a global positioningsystem or camera.
 22. The computer of claim 18, wherein said computer isa global positioning system or camera.